Stable biologically active chlorinated phenol composition



fin 'the form of crystalline solids. r v

' is beneficial to havei the various halogen substituted phenols in the form of stable concentrated solutions. When commercial grades, of halogen Substituted phenols are dissolved in alkaline 2,925,361 r r TABL E BIOLOGICALLY ACTIVE) CHL YRINATED PHENOL ,co Posrno Carol H. Bollenback, Maywood, Ill., assignor to Nalco Chemical Company, Chicago, 111., a corporation of Delaware N Drawing ApplicationDecember 10, 1956 i Fi9lNr 6 .72??? 5 Claims- (c am-p31),

This invention relates to a liquid extraction process for the removal of insoluble impurities contained in commercial grades of halogen substituted phenols. It is particularlyconcerned with new, chemically stable solutions containing'halogen substituted phenols.

Halogen substituted phenols comprise a group of compounds having a wide variety of useful properties. These Chemicals are well known for their ability to control'and inhibit the growth of numerous species of microorganisms.

They are used as biologically active agents in such industries as the paper, lumber, textile and agricultural ingredients. 1 Similarly, other'halogen substituted; contain inert, impure-ingredients'which tend to tate from solutions'prepa red'i therefrom. A certain centage of these :inert ingredients is usually .insolub e rn' active chemicals it is extremely advantageous if 'th'ey 'are combined with certain other :materialsto; rende most polar solvents. V w I In using halogen substituted phenols as biologically controlling microorganisms in industrial process waters.

Other objects will appear hereinafter.

In accordance with the invention it has been found that'insoluble impurities contained incommercial grades industries and have beenaccepted as valuable aids in s the prevention of waste and decay caused by the uncontrolled growth of' microorganisms. These compounds are P u ar fis tivs in gqntrs l nsmie sqr ni m found in cooling towers and in. water used to recover petroleum secondary water flood opelr ations.

one of the a 3 E P1.?PP, i? QP. ZQPE Z? vah iwl is the n r .ia vtt s rin etsuit imit and protect against molds, slimes and fungi ofalljypes.

When halogen'fsubstit uted phenolsfare emp industrial processes it isus u'ally the, practice to use tech-1 meat or commercial grades 'Cher'nical refiningor pa fication of halogen substituted phenols int he manu facturing process would place an"incre ased co st o'nthe product. Commercial grades are satisfactory'in-Ymost case'ssince the products may be" used as supplied-{usually Insornec'ases, however, t

polar'liquids such as watefand/ or alcohols the solutions will tend to throw out impurities in'the form gof'crystfals -oi fine particles whichoften act to precipitate active halogen substituted phenols. These: impurities tend not of halogen substituted phenols may be removed from polar solvent solutions of these materials by'treating'such solutions *witha minor, yet effective amount, of, an aliphatic petroleum naphtha. By using-sucha solventcxtraction technique, concentrated chemically stable solutions canbe easily and conveniently produced.

The various halogen substituted'- phenols,y containing insoluble manufacturing impurities, that may bejnsed in t e rpmin t -i Y 9 -inli s Suqh. subs tu n s, -h 0 r h t2 .ram-chlsm h 'ol 2A:

,di h a hsn l F 38 ?fi ichlbro hsn ln2.4.6 -'t ch 9. 9- 1 P en .3, .6- e ach orop no pentac rophen 4- l t -c hi -hl r :3 5-? 3 1e anemia-ch o aortho-beuzylphenol. ,Theother well known substituted rhe a We a h "so e por d n o odo an gfiuoro-substituted phenols may be used. A

accomplished by adding with thehalogen substituted phenol'alkali such as an alkali metal hydroxide into the ,solventin a stoimetric amount; The pH of the resulting 7 solution should then be adjusted to give a pH of at;1east 8. The solutions produced by the practices of the present inventidnhave a pH of-atleast 8-and-preffid'fe'rably a pH offrom 1 1.5to 13.5. only'to make thesolutior'i unattractive but are not accepta'ble tomost industrial users;

The 'irripurit-iescontained in halogen substituted phenols are for the most part inorganic-*salts 'su'ctr as' so'dium *surraieana thesalts offsuch'm'e'tals as copper ahd'alumi- *n'um. Depe'nding upon the particular manufacturing iproc'es'sjemployd, the impuritiesmayFiiot or'ily being or anic salts-but m'a'y' bemetal complexes oif 'or'ganic sparing the'solvent'combination, good results are'obtained i by using either diacetone-qalcoholfor anfalcoholfof th e materials. 'For a complete discussion of the variousfrnan ufacmring processes for the;several halogeii substituted phenols see Encyclo edia ofche'micar T chnology? 7 vet 10, p. 317 et subs., lnterscienc e;Publishers; 195 33 I Byanalysiscommercial g'r'ad'es of' halc'g phenols shave impurities resentias biologica V V ponents ranging from about 1 by we'ight'to as much as :1 5 byweight. Thusfa typical, technicalgrade'of pentachlordphenol contains 83%by weight-ofpure'penta- 'chloro'phenol, 12% of other ."r'nixe'd chlorinated phenols and 5% of inert ingredients." [Thedr'y sodium s'alt'of a commercially available p'entachlorophenol was found to -contain 7 5% by weight lof sodium 'pentachlorophenate,

113% of otherisodium chlorophenates and' 1 2% of 'inert stable concentrated solutions of the invention comprise amixture .of, a YQIQIQSOQhlbl alcohol' and soft water. ,These ;solve'ntsj.may. .be.combined in: a weight ratio-of alcohol,tofwater of'j'from l4:5 .to:4f:'15 and preferably 213.;

LWhil any water-soluble alcohol may housed in prei where R is frorn the group consisting of. hydrogen an d lower alkylgroupsqf from ,1 t,o ,,6 carbon at length, n is anintegerof from 2 toyflfan'd'xi h of from-liod. as

Examples of such alcohols areethylene glycol, propylene :glycQLbutylene glycol, .diethylene' glycol, triethylene vglycol and the higher water soluble 'polfyortyalkylene- "glycols such as the several polyoxyethylene, polyoxy-f .propyleneand polyoxybutylene glycols as'well as heteric mixtures thereof.

V EspeciaIly 'g'o'odcofsolvent alcohols are the lower alli'yl :ethefrs off glycols and polyoxyalkylene-glyco1s2 Several l Io solnbilizethe halogen. substitutedphenolsin'polar solvents such as:water or alcohol it is necessary to preparethe alkali metal phenates. This ismost conveniently 'I'he polar solvents found most useful in preparing-the I illustrative compounds are diethylene glycol monobutyl Pounds per gallon at 25 C. 7.87 Refractive index at 25 C. 1.416 Flash point p F 134 Viscosity at 25 C..(centipoises) 1.0-5 four point F.. 121 Specific gravity at 25/25 0. 0.943 0.945

The soft water may be prepared by either distillation or by-ion exchange techniques and should not have a total hardness (as CaCO exceeding /2 grain per gallon "and preferably not more than 1 part per million. It was foundthat when water, such as Chicago tap water, was used to prepare compositions of the invention undesirable solution cloudiness occurred.

When commercial grades of alkali metal halogen substituted phenates are added to solvent mixtures of the types described and the pH adjusted to between 8 and 11.5 the impurities from the phenates begin to separate in periods of time, ranging from a few minutes to as much as a few days, depending upon the ingredients used, temperature and the particular solvent chosen.

It was found that these impurities could be rapidly removed by adding to the solutions from 2% to and preferably 3% to 4% by weight of an immiscible aliphatic petroleum naphtha. Aftera slight mixing period the treated solution is allowed to stand for a period of time sufficient to permit the naphtha to rise tosthe top of the solution. Contained in the naphtha layer are the topnaphtha layer by appropriate drainage techniques,

'jcentrifugal separation or filtration.

The solvent immiscible aliphatic naphthas include petroleum distillate solvents having boilingranges from about 110 to 400 Rand an aromatic content not ex- "ceeding They include such productsas Stoddard solvent,.varnish makers naphtha and rubber solvent naphtha which is distilled from a parafiln base crude. -Of these solvents the best results have been obtained using Stoddard solvent.

As will be shown later, in some instances it isdesir- -ableto incorporate into the finished liquid solutions a m nor amount of a non-ionic watersoluble wetting agent. -'As an aid to preparing the compositions of the invention there is listed below a general formula of the in:

gredients used.

In the above formula the non-ionic wetting agent is .311 optional, yet .desirable ingredient. When it is, not

included in the composition a compensating amount of water'soluble alcohol or soft water may he used.

In order to further illustrate the formulating techniques that may be employed, the following is given'by given.

impurities which may be separated from the mix by 'decantation; withdrawal'of the finished solution from the way of example.

Example I The chemicals listed below constituted a charge to a reaction vessel fitted with an outlet at the bottom thereof and a mechanical stirrer.

Chemical Percent by Weight w enact-wa on The chemicals were added and mixed in the order The chlorinated phenols were not solubilized until the potassium hydroxide was added. After all the ingredients were mixed the product was allowed to stand for 4 hours. During this time fine dust size particles floated to the top of the mixture with, and were entrained in, the Stoddard solvent. The remaining clear brown liquid product was withdrawn from the bottom of the vat. The product was stable and microbiologically active after 9 months of storage at room temperature.

The physical characteristics of the finished product were as follows:

Color Amber.

Specific gravity at 60 F. 1.164.

Flash point (Cleveland open cup) Boiled at 205 F. Fire point 212 F.

' Cloud point (ASTM) a- 11 F.'

A sample of this batch was stored at 8 F. for 12 hours, then allowed to warm to, room. temperature, cooled again, etc. After 10 changes oftemperature and 4 weeks of storage the formula showed no evidence of clouding or precipitation.

Another sample of the above product was used to test the corrosiveness of the formula. Small steel and brass coupons of the grades used in shipping containers and fittings therefor were submerged and partially submerged in the test solution under conditions simulating actual drum storage and use patterns. The corrosion rate on the partially submerged steel coupon was 2.4 mils per year. For the fully submerged steel and brass coupons it was 1.1 and 1.6 mils per year, respectively. No gas formation was evident.

For purposes of comparison the same formula was prepared without using Stoddard solvent.

invention possess outstanding characteristics when used to control microorganisms. By incorporating into the formula 2% to 10% by.weight of a non-ionic wetting 'agent the utility of the formula is multiplied since better surface contact of the active chemical with the object to be treated is achieved. When used to treat microorganisms the non-ionic wetting agents increase cell permeability and allow the halogen substituted phenols to more readily enter the cell wall and act upon the intercellular components, including the cytoplasm and the mitochrondrial body. When liquid formulae containing non-ionic. wetting agents are used to treat accumu- Precipitation was evident within 3 to 7 days and the product was not lated masses of slime and fungi. such as com .only occur in paper rnills, the wet tling fage'n't disperse these massesinto the system in thi form of fine no operation of machinery used in thepapermaking process.

A comprehensive list ofnon-ionic,wctting' agents is given in the publication," Synthetic Detergents, Up to Date, by John W. McCutcheon, soap andssaniitary Chemicals, July-October 1952-.- M r Liquid formulations of the invention containing as their H e in ated particles and .prevent'thefsloug hing Of; the masses in Y the form of large pieces'fwhich often interfere with the biologicallyactive ingredients a mixture of pentachlor($- phenol and 2,4.5-trichlorophenol, as their alkali metal salts, give outstanding and surprisingly unexpected results when used in the treatment of industrial process waters to prevent and mitigate slimes,'molds and fungi commonly occurring in such'syste'ms. For the best results it is desirable to combine the alkali irntal pentachlorophenate and alkali metal"2,4,5-trichlorophenate in a weight ratio of from 1:1 to 4:1 and preferably 2:1- A very desirable formulation is achieved by combining from 2% to 10% by weight of a non-ionic wetting agent of the type described. in the formulation. Thus, a typical, highly I potent formula might be prepared using the general com- To illustrate the beneficial effects of the combination of alkali metal. pentachlorophenates, 2,4,5strich1 rophenates and non-ionic. wetting-agentversusalkali-metal pen-'- taohlorophenates alone. theinextiexample is lg Ys The test method was essentiallya U.S.D.A. phenol coefiicient test procedure with the sampling times being 1,

- 6 and 24 hours, respectively,with subculturing being made at the same time. The test organismswere Aerobacter aerogenes, Aspergillus niger and Monilia.

The results were recorded in terms of parts per million necessary to achieve a total kill on the test organisms at a culture media pH of 5.0. The sodium pentachlorophenate was compared with equivalent amounts of potassium pentachlorophenate and potassium 2,4,5-trichlorophenate as contained in the formula prepared in Example I; The results of these tests are listed below in Table I.

TABLE I v A. SODIUM PENTACHLOROPHENATE Hrs. A. urogenes A. niger Monilia B. COMPOSITION- 0F XAMPL 1 example is given.

Examp le Ill The-liquid productprepared in Example I-wassubjected to several tests to furtherprove its elficacy.

One method employed was that described by,Bollenrt 1 i l A.-"z,leroge nes in a contact time' of 011 h Al ght '1 if v "the ave m l nin-p -lof e as veq mps. .d

iTd m ne u e o ulum pr par d'by admstm n '1 hour broth culture of aerogenesv to appi'oximately two million organisms perfrnhin distilled water immedis y b sr i he t t- The ad u ed ltu e u within five minutes afteriits preparation and the test ca ried out with one of 40.1% steels ennui 91th; chemical to be tested. Thismethod establishes a killing range for the chemical tested.' r I To determine the microbiologicalinhibition properties of the formula prepared in Example I, a gas tube method was used. In this test the culture medium used consisted of 24 grams of dextrose, rgriambf Basarninbact I ical to be tested was introduced using an appropriate concentration of stock chemical to avoid more than a 5% ted. In mixing, each tube was inyentedin as to fill-the upright closedend of the tube With ctest liqui The ubeswere incublaledia 3lO.IQ-.. Z.4 hQ 1S- each tube and inoculatedtina subculturc tubecontm 'ng '10 .ml. of steril'e. nutri I y w error in final dilution. For this purpose the volume of chemical introduced should be 1' ml. of less. The chemical and the inoculated medium were mixed gently. A control test was also in which the che Twas (imitch a 'n'ranner At the end of l hour contaotand again after '24'hou'rs contactza loopful of-the test mixture was withdrawn from h... 11 s uhs t Qr- 8 hour and ,were incubated at-3,7

was recordedat 48 hours.

The results obtained, aswell as other characteristics are shown in TableII below:

TABLE II TEST PERFORMANCE A. aerogencs:

' 1 hr. plate kill 125-250 p.p.m.

Gas tube test-.. pH 5 7 pH 8 1 hr, kill 100400 200 24 hr. kill 50100 200 Tn'hihitinn- 50-100 100-200 Adsorption by Fiberype'rcent V A. niger: v

Gas tube test; H 5 pH 8 1 hr. kill 200 200 24 hr. kill 1 25-50 200 Inhibition.-. 10-25 25-50 stable under normal conditions of use and are ideally V suited for use-in treating many'industrial process waters.

j; In the specificationfandclaims the expression alkali metal halogen substituted phenates or its equivalent has "been-used with; referencef-to.weightpercentsinlconjunce g I V e "t'ion with-formulae mathpreparation or-ror une. It To further demonstrate the microbiologioal'activity 0r if si dfh h weights were e the liquid formulations of the inventionfthe following welght ofjthe Potassium} salts and e h 'a k metal V v salts are employed equivalentweighlts should be used.

-- The term biologically active agent as usedrherein is meantto define a 'sub'stance or material which will act to The invention demonstrates a new andlus eful method back and Cruickshank in Analytical Chemistry, vol. 16 of preparing chemically stable, biologically active cont-j growth. Theresults of these tests indicated 1 and 24 hour killing ranges. The gas production for inhibitionleyel =-7 positions. It has been the experience of the art that whenever concentrated solutions of commercial grades of halogen substituted phenols are prepared precipitation occurs. By. removing the inert impurities from'the solutions, a desirable stable liquid product is afiorded which is of great value to many branches of industry.

The invention is hereby claimed as follows:

. 1. A chemically stable, biologically active liquid having a pH of at least 8 comprising Ingredients Percent by Weight A. Chlorine substituted alkali metal phenate from the group consisting of sodium and potassium chlorine substituted phcnates 15-35 B. Water Soluble Alr-nhnl l664 C. Soft-Water" 25-75 said liquid having been formulated with commercial grades of chlorine substituted phenols and an amount of an immiscible aliphatic petroleum naphtha suflicient to remove the insoluble impurities from said liquid, the said immiscible aliphatic petroleum naphtha containing such impurities having been removed during formation. 2. The composition of claim 1 wherein ingredient A is a chloro-substituted potassium phenate.

3. A chemically stable, biologically active liquid having a pH of at least 8 comprising Ingredients 'Percent by Weight;

A. Chlorine substituted alkali metal phenate from the group consisting of sodium and potassium chlorine suostituted phenates 15-35 28. Water soluble alcohol 20-60 0. Soft water 25-75 D. Non-ionic disperant 210 said liquid having .been formulated with commercial grades of chlorine substituted phenols and an amount of an immiscible aliphatic petroleum naphtha sufiicient to remove the insoluble impurities from said.liquid, the said aliphatic petroleum naphtha containing such impurities having been removed'during formation.

4. The composition of claim '3 wherein ingredient A a is a 'chlorosubstituted potassium phenate.

5. The composition of claim 3 wherein the chlorine substituted alkali metal phenate is a mixture of alkali metal pentachlorophenate and 2,4,5-trichlorophenate from the group consisting of sodium and potassium penta- 10 chlorophenates, combined in a weight ratio of from 1:1

to 1:4 and the water soluble alcohol is from the group consisting of diacetone alcohol and an alcohol of the formula where R is from the group consisting of hydrogen and lower 'alkyl groups from 1 to 6 carbon atoms in chain length, n is an integer of from 2 to 4 and x is an integer of from 1 to 4, said water soluble alcohol being present with the soft water in a Weight ratio of from 4:5 to 4:15.

References Cited in the file of this patent UNITED STATES PATENTS Jan. 1, 1955, pp. 1-3.

Atlas Spans and Atlas Tweens, Surface Active Agents, November 1942, pp. 4 and 7. i

Glycols, Carbide and Carbon Chem. Corp, Mar. 31, 1947, pp. 1 and 6. r

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No; 2 925 36l February 16; 1960 Carol H Bollenbaek It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2 line 60 the formula should appear as shown below instead of as in the patent:

column 7 line 36 in the second table,- first column thereo? last line for "disperant"; read dispersant Signed and sealed this 29thday of November 1960,

(SEAL) Attest:

ROBERT C. WATSON KARL H, AXLINE Att ti Oifi Commissioner of Patents 

1. A CHEMICALLY STABLE, BIOLOGICALLY ACTIVE LIQUID HAVING A PH OF AT LEAST 8 COMPRISING 